Luminous composition of matter and method of producing same



Patented Sept. 27, 1938 PATENT. OFFICE 2,131.55") LUMINOUS COMPOSITION OF MATTER AND METHOD OF PRODUCING SAME Jeremiah F. Goggin, Davenport, Iowa No Drawing. Application March 30, 1936, Serial No. 71,794

1 Claim. (Cl. 134-47) The present invention pertains to the production of a luminous composition of matter and the product resulting from the practicing of the process herein described. Among the objects of this 5 invention are the production of a highly luminous product; the economical production of a product of the nature indicated; an improved method of producing a luminous composition of matter with the object in view of having a highly luminous.

product; and such further objects, advantages, and capabilities as will hereafter appear and as are inherent in the process and product herein disclosed.

Phosphorescent products and various methods of producing them are already known but I have, by diligent investigation, discovered a new method of producing such products which results in a .more highly luminous substance and one which holds its luminescence for a longer period of time. Broadly speaking, my invention comprises combining in proper proportions and under proper conditions hydrated lime or alkali earth hydroxide or carbonate; 9, liquid solution of lithium salts, such as nitrate; a liquid solution of bismuth salts, such as chloride; a liquid solution of chromium, molybdenum, uranium, or tungsten salt and sulphur, or their equivalents. The proportions of these substances may vary considerably and the luminescence will likewise vary. The process of combining these substances is more critical than the amounts thereof Variations from the substances named above willbe stated hereinafter, the present statement being intend ed merely as illustrative.

The following is given as illustrative of the materials used in producing one form of the substance herein referred to:

Hydrated finishing lime containing about ten The amount of iron content in the above.

chemicals must be small.

The hydrated lime and barium hydroxide may be and preferably are used in the powdered form, while the bismuth nitrate, sugar, and lithium nitrate are dissolved in water, as set forth here- Barium hydroxide, Ba(OH) 2.8H2O, generally inafter, and added to the mixture of 1 hydrated lime and barium hydroxide. Y

The solutions mentioned are best kept in containers provided" with means whereby the solutions may be readily drawn from the containers as desired. The bismuth nitrate crystals are'dissolved in water to make a solution having a concentration approximately equivalent to twentyfive milligrams (25 mg.) of the nitrate to one cubic centimeter (1 cc.) of solution. Of course, in preparing the solution, one would not want to use these quantities, but they are given merely as illustrative of the proportions used. In pre paring the solution, a quantity of the crystals in excess of the amount needed should be powdered and then the requisite amount should be weighted out. Twenty-five grams (25 g.) of the powder is then dissolved in about twenty cubic centimeters (20 cc.) of dilute nitric acid (1:6) and several. hundred cubic centimeters of water. If a white precipitate isproduced, additional acid must be added to clear up this precipitate, as it is necessary to use sufficient acid to prevent the bismuth nitrate from hydro-lyzing and precipitating as the I pletely dissolved, wateris added to make a total of two (2) liters of solution, and then this is placed in another container'for storage until, needed. I

The lithium nitrate solution is prepared by dissolving two hundred fifty grams (250 g.) of the powdered nitrate in about eight hundred cubic centimeters (800 cc.) of water, and then, when completely dissolved, sufficient water is added to produce a total of one liter.

This will give approximately a twenty-five per cent (25%) soluparing six pounds (6 lb.) of this luminous sub stance are preferably approximately as follows:

, Grams Calcium oxide (hydrated)' 2,0 16, Barium hydroxide 1,088

Bismuth nitrate 96 cc. of solution 1 2.4 Sugar"; 320 cc. of solution Lithium nitrate 16'l cc. of solution 41,8

Sulphur 64 0 powder is stirredthoroughly in order to assure the sulphur being thoroughly mixed in. Since the mixture is not finely ground to start with and the sulphur is, there is a tendency for the sulphur to nfn'urunfn ea the grinder first. This makes it necessary Bismuth nitrate that the ture be thoroughly stirred after Sugar 405 the n in operation 15 completed. Another i 1E}; procedure is to add the sulphur in small quansulphur i tities as the grinding proceeds.

This figures up to a little more. than one hum.. dred per cent (100%) but the percentages given are only approximate and this slight variation'is not enough that it need disturblahyone. e I

The approximate limits for the typical example given above are about as follows: g

CaO 49. -5? Ba(OH)2.8HzO 25.6 29.6 Bi noo 0.05. 0.07 -E s, 4 -5 1 :5 LiNO3 1 .2 s 14 to form a thin-paste.. Abetter mixture may be produced by bringingthe liquid toa boil and stirring. for several minutes This is :bestdone in a container having. a glazed surfacasuchas a gran.

iteware pan. To thispaste is added, slowly and with. constant. stirring, ninety-six cubic centimeters (96%.) ofthe bismuthnitrate solution.

It is important that this be added. slowly and that. it be stirredconstantly until a complete and thorough mixing has been accomplished.

7 It is immaterial whethenthesugar or the lithium' nitrate isjadded next but. we willrassume the addition of.th'esugar.- This requires. the addition of, three hundredtwenty cubic centimeters (320 cc.) of the sugarfsolution, if the product is being prepared-in accordance'with the first table given above. This sugar. solution shouldbe added. slowly and,stirred in well. in-orde'r..to produce aunt-- form mixtures After this," -the.lithium. nitrate solution may be. added, slowly and .with .constantstirring, in order to prevent the formation. .of.

the hydroxide which wouldbe precipitated and would prevent the formationeof-ea uniform mix-,. ture. The foregoing accoun'tsiOr everything but. the sulphur, and this isto'be added at alaterstage in theprocess.

7 mixture be stirred to prevent spattering and to:

assure homogeneity of the mixture. Sinceit is very difiicult to completely cleana container-in which a quantity of the-mixture has been dried} itis preferable that the mixing and drying be done in different containers in order to keep one. cleanzfor the. mixing operation. As thedryne'ss' progresses, the paste becomes stiff and lumpy.

The lumps should be brokenupv asmuch as.possi-.

ble to fabiIitate the drying.

When the. mixture is dry," the required amount 3 of .sulphuris added and the mixtureis ground to a very fine powder. The finer and moreuniform themixture, the more uniform will'be the result The powder-{produced as above set forth, is

This container is preferably a graphite crucible. The No. 8 size will holdi-alittle over two pounds (2 lbs.) of the powder and is probably the most satisfactory as it permits'a more uniform heating than would a larger size. The process is more or less critical in "the matter'of heating as a variation intemperature in excess of twenty degrees (20) above or below the proper amount is likely to cause partial or complete failure of the process. Also, the period-of heating is more or less critical.

This description is given with reference to the pyrometer' at Saint Ambrose College, Davenport, Iowa, and any other pyrometer, in order to give accurate results, should be calibrated with'this one todetermine changes in temperature readingsneeded to 'securethe best results. The readings'of this pyrometer are correct according to ordinary methods of calibration, and it possesses the usual accuracy.

Beforethe'mixtureis placed in the furnace, the temperature of the'furnace shouldbe'brought to ninehundred'degrees"(900) an'dit should be maintained within not to exceed twenty degrees (20) of this point during the time of heating. Any'suitable heating means may be used, pro vided" a reducing atmosphere? is maintained in the'heating chamber. For two pounds (2"lbs.) of mixture in a'No. 8 crucible, the heating period is from two and one-fourth (2%) to 'two'and one half (2%) hours." Larger crucibles will require experimentation'to"determine the exact period of heating requi'redtto produce the'best results. If'a" No. 5 crucible; contain'inga smaller amount of'the mixture, isused, thetime'maybe reduced to from*'forty-five'(45)'to sixty (60) minutes. The degree of finenessof'the material is also a determining factor'in the length of time required. Since' graphite crucibles are fragile, it" is necessary that they be handledc'arefully'. lfiproperly handled, 'they'williwithstanda great number of heats but thegrajphite is gradually. oxidized" and only the fireclay base remains. For this reason, the crucibles become'brown'after oneior two heats.

After the heating-has been completed, the crucibles; should be removedi'frorn the furnace and covered with apiece of asbestos to-prevent oxi'datiom of the material. .They should then be set in as=cool a place as possible and allowed to remain undisturbed until cool: This may require one or two hours, dependingupon the method of cooling? When the coolingihasi been completed,

the top layer of oxidized matter" is tobe scraped away-until the surface-exposed is auniform yellow color.-- The phosphorescence -of=the exposedsur-- face isthento-be tested;- -If it-shows a uniform bright blue color, the heatingtemperature and timehave -proba'bl-i b een correct. However, be fore turning out the sulphides,--the-upper-three fourts: inch /t' in-.-)* should lee-removed and the new.--surface--'again'tested: If it appearsto con-' sistof two layers with theinner .cor-e'luminescing only poorly; the heating-time rhas been too short. a

ing phosphorescent material. After grinding, the" The outer layer may be recovered by cautiously separating it from theinner' layer. This is'not difficult as the two layer's tend to 'cohere quite well. Re-heating of the center portion is of no value, and this must be regarded as wast'e'm'a nitrate is'ilSbdas an activator. As substitutes for this, inwhole' or in part, equivalent quantities of basic substances: such as coppernitrate (Cu(NOs)z)',' manganese-chloride. (MnClz), ru-

I have by no means named all of the substances which have been tried and found to work, nor is it possible to give, within reasonable limits, all of the operating conditions for all of the combinations of substances which may be combined terial. If it is the outer layer? which is poor in bidium nitrate (RbNOa), caesium sulphate 5 luminescence, it is an indication of too higha (Cs2SO4), and chromium chloride (CrCh); may temperature or too long a period of heating. It be 'used. Also',-,acidic substances may be used, l is for this reason that the temperature and time such as sodium chromate (NazCrOi) potassium of heating must be so closely watched throughout molybdate (K2M004) and sodium tungstate 7 this entire period of heating. r (NazWOrl). 10

While still hot, the sulphides will luminesce" The lithium nitrate, in the typical example with a green color which becomes blue as they given above, was used as a flux. Other fluxes, cool. Various procedures have been followed in such as mo-lybdates, carbonates, nitrates, borates, an effort to determine what is the'most desirable phosphates, ohromates, tungstates, chlorides, and practice for the production of the best results. sulphates of alkali metals and alkali earth metals Several of these have had to be'discarded as may be'subs'titutedin'equivalent'amountsfor the" worthless or even harmful. As an illustration; lithiurn'riitrate. 5 I I the barium and calcium hydroxides were' pre-' In the typical example, the sugar'serves as a heated atatemperature varying-from six'hundr'ed binder and as a reducing agent; Equivalent to e ht dred degrees (600-800) but this quantities of such c'arbohydratesas cellulose-and yielded a less satisfactory result- Also, covering" glucose maylbe-used,"as' may alsoan equivalent the crucible with a tight fitting fireclay plug prequantity of ground carbon. 3 r i vents theescape or the excess sulphur and the The sulphur maybe replaced, in whole or in result is not s oo If h s ph is mixed part, by equivalent quantities of selenium (Se) wi h t W p before ry n it i readily and tellurium (Te). The resulting product will 25. taken up to form polysulphides which are decombe a luminous selenide'or telluride instead of a posed when heated to the temperature required sulphide. by this method. This gives a perfectly uniform By a proper choice of materials and operating distribution of the sulphur but for some reason conditions, blue, red, and colors intermediate bethe same results are not attained as by following tween 1 and red have been produced For the method described above. There is no adexample, the color green has been produced byvantae in us n t s procedure a in fact, the use of the following mixture and proceeding y e ded a poorer product. as for blue: Strontium hydrate, bismuth nitrate, It has been indicated above that the materials Sodium tungstate, lithium nitrate, andsulphun us d y be Varied When the materials are The percentage limits of these substances and for varied, it necessitates corresponding changes in th lik satisfactory results appear t the temperature. It is believed, however, that b t as follows; for a satisfactory product, the maximum tempv erature is approximately one thousand degrees ggggg f' 25 g 29 centrigrade (l,000 0.). Similarly, the lower g'fi' ,"'".""f" 0'381 40 limit for satisfactory results appears to be ap- LiNO 2 "f"" 341 381 proximately seven hundred degrees centigrade s 3 ""1, I (700 0.). However, it is possible that mixtures not yet tried might prove that these limits should The following table repeats the two typical exbe altered. The degree of fineness of the mixture amples given and indicates the substitutions to be heated will alter both the time and the which may be made for the substances given in temperature of heating. the typical examples.

g figg Activators Reducers I Fluxes 5553? Blue 0210. Bi(NO:) .5HrO. Carbohydrate. LiNOa. s.

Ba(OH)z.8Hz0.

Green Sl'(OH)2.8HzO. Bi(NO );.5H2O. Carbohydrate. LiNOa. j S.

Substitutes Oxides, hydrox- Ou(NOa). Carbohydrates Molybdates, carbonates, ni- Se.

ides, carbonates MnOlz. such as sugtrates, borates, phosphates, To. of RbNOa. ars and celluchromates, tungstates,

Sr. CSzSOi. loses. chlorides, sulphates-of a1- Zn. ClCls. kali metals and alkali 0d. NazOrOo earth metals. Ra. KzMooi.

Na2WO4- I .65 In the variation of materials referred to above, In this specification and the appended claim, the calcium and barium compounds may be rethe expression Luminescent formers is used as placed in whole or in part by equivalent amounts the equivalent of Lu-minaphores and the word of such materials as the basic oxides, hydroxides, Reducers is used as the equivalent of Reducin and carbonates of strontium, zinc, and cadmium. agents.

to; produce a satisfactory product. I; I have; how-:

ever, indicated a typical example and n-in dic'ated how variations of substances, temperaturea-finee ness of powder, and time of heating may modify the results which are evidenced by a product having a greater or less phosphorescence. In view of the number of variables and-the amount of vari-' ation which may occur, I do not wish to be limited to any particular proportions of the substances used, since these may vary with the substances chosen. Also, as indicated above, the temperatureand time of heatingmust vary withthe substances used and the proportions thereof.

It is of course understood that the specific disclosure given above may be departed from without departing from the spirit of this invention as set forth in this specification and in-the appended claim.

Having now disclosedby invention, I claim: The method of producingphosphorescent maa terial-which comprisesmixing dry hydratedxcah cium oxide and dry barium hydroxide, both in powdered form, in the proportion'of'iorty-nine (1 to 2 parts'of lithium nitrate; evaporating themixture to approximate dryness, the mixture being stirred whiledrying; reducing the dry mixture to a powder; adding to-the dry mixture fourteento eighteen (14 to 18) parts of sulphur in powdered form; grinding and mixing the mixture; and heating the mixturein a reducing atmosphere at a "temperature of approximately nine hundred degrees centigrade (900 C.) for 20% approximately three (3) hours.

JEREMIAH F. GOGGINQ 

